Method for producing fluorovinyl ether compound

ABSTRACT

An object of the present invention is to provide, for example, a novel method for synthesizing a fluorovinyl ether compound from a fluorine-containing vinyl compound. This problem is solved by a method for producing a compound represented by formula (1):whereinRa1 is a hydrogen atom, a halogeno group, an alkyl group, a fluoroalkyl group, or an aromatic group optionally having one or more substituents,Rf is a fluoro group or a perfluoroalkyl group,Ra2 is a hydrogen atom, a halogeno group, an alkyl group, a fluoroalkyl group, or an aromatic group optionally having one or more substituents, or(i) Ra1 and Ra2, (ii) Ra1 and Rf, or (iii) Rf and Ra2 may be linked to each other,Rb1 is Rs,Rb2 is a hydrogen atom or Rs,Rb3 is a hydrogen atom or Rs, ortwo or three of Rb1, Rb2, and Rb3, taken together with the adjacent carbon atom, may form a ring optionally having one or more substituents, andRs, in each occurrence, is the same or different and represents a hydrocarbon group optionally having one or more substituents, the method comprisingstep A of reacting a compound represented by formula (2):whereinRx is a leaving group, andother symbols are as defined above,with a compound represented by formula (3):wherein the symbols in the formula are as defined above,in the presence of a transition metal catalyst.

TECHNICAL FIELD

The present invention relates to a method for producing a fluorovinylether compound.

BACKGROUND ART

Examples of conventionally known methods for synthesizing fluorovinylethers include substitution reaction of a fluorine-containing vinylcompound using a strong base (e.g., Patent Literature (PTL) 1,Non-patent Literature (NPL) 1, and NPL 2).

However, a method for synthesizing a fluorovinyl ether from afluorine-containing vinyl compound at a high yield has not yet beenreported.

CITATION LIST Patent Literature

-   PTL 1: U.S. Pat. No. 2,799,712

Non-Patent Literature

-   NPL 1: T. M. Sokolenko et al., Chemistry of Heterocyclic Compounds,    2011, 46: 1335-   NPL 2: Pieter J. Klein et al., Nuclear Medicine and Biology, 2017,    vol. 51, pp. 25-32

SUMMARY OF INVENTION Technical Problem

An object of the present invention is to provide a novel method forsynthesizing a fluorovinyl ether compound from a fluorine-containingvinyl compound.

Solution to Problem

As a result of extensive research, the present inventors found that theabove problem can be solved by a method for producing a compoundrepresented by formula (1):

whereinR^(a1) is a hydrogen atom, a halogeno group, an alkyl group, afluoroalkyl group, or an aromatic group optionally having one or moresubstituents,Rf is a fluoro group or a perfluoroalkyl group,R^(a2) is a hydrogen atom, a halogeno group, an alkyl group, afluoroalkyl group, or an aromatic group optionally having one or moresubstituents, or(i) R^(a1) and R^(a2), (ii) R^(a1) and Rf, or (iii) Rf and R^(a2) may belinked to each other,R^(b1) is R^(s),R^(b2) is a hydrogen atom or R^(s),R^(b3) is a hydrogen atom or R^(s), ortwo or three of R^(b1), R^(b2), and R^(b3), taken together with theadjacent carbon atom, may form a ring optionally having one or moresubstituents, andR^(s), in each occurrence, is the same or different and represents ahydrocarbon group optionally having one or more substituents, the methodcomprisingstep A of reacting a compound represented by formula (2):

whereinR^(x) is a leaving group, andother symbols are as defined above,with a compound represented by formula (3):

wherein the symbols in the formula are as defined above,in the presence of a transition metal catalyst.The present invention has thus been accomplished.

The present invention includes the following embodiments.

Item 1. A method for producing a compound represented by formula (1):

whereinR^(a1) is a hydrogen atom, a halogeno group, an alkyl group, afluoroalkyl group, or an aromatic group optionally having one or moresubstituents,Rf is a fluoro group or a perfluoroalkyl group,R^(a2) is a hydrogen atom, a halogeno group, an alkyl group, afluoroalkyl group, or an aromatic group optionally having one or moresubstituents, or(i) R^(a1) and R^(a2), (ii) R^(a1) and Rf, or (iii) Rf and R^(a2) may belinked to each other,R^(b1) is R^(s),R^(b2) is a hydrogen atom or R^(s),R^(b3) is a hydrogen atom or R^(s), ortwo or three of R^(b1), R^(b2), and R^(b3), taken together with theadjacent carbon atom, may form a ring optionally having one or moresubstituents, andR^(s), in each occurrence, is the same or different and represents ahydrocarbon group optionally having one or more substituents, the methodcomprisingstep A of reacting a compound represented by formula (2):

whereinR^(x) is a leaving group, andother symbols are as defined above,with a compound represented by formula (3):

wherein the symbols in the formula are as defined above,in the presence of a transition metal catalyst.

Item 2. The production method according to Item 1, wherein R^(a1) is ahydrogen atom.

Item 3. The production method according to Item 1 or 2, wherein R^(a2)is a hydrogen atom or an aryl group.

Item 4. The production method according to any one of Items 1 to 3,wherein R^(b1) is a C₁₋₁₁ fluoroalkyl group, R^(b2) is a hydrogen atom,and R^(b)3 is a hydrogen atom.

Item 5. The production method according to Item 4, wherein R^(b1) is aC₁₋₁₁ perfluoroalkyl group.

Item 6. The production method according to any one of Items 1 to 5,wherein R^(x) is a halogeno group or a sulfonic acid ester group.

Item 7. The production method according to any one of Items 1 to 6,wherein the transition metal catalyst is at least one member selectedfrom the group consisting of palladium catalysts, copper catalysts,nickel catalysts, platinum catalysts, and iron catalysts.

Item 8. The production method according to Item 7, wherein thetransition metal catalyst is a palladium complex.

Item 9. The production method according to any one of Items 1 to 8,wherein the reaction of step A is performed in the presence of acoordination compound.

Item 10. The production method according to Item 9, wherein thecoordination compound is a biphenyl compound represented by formula(4-1):

whereinA⁴a is a benzene ring,A^(4b) is a benzene ring,R^(4a1) is a phosphino group substituted with two C₁₋₂₀ hydrocarbongroups,R^(4a2) is an alkyl group or an alkoxy group,R^(4a3), in each occurrence, is the same or different and represents asubstituent,R^(4b), in each occurrence, is the same or different and represents asubstituent,n4a is a number of 0 to 3, andn4b is a number of 0 to 5.

Item 11. The production method according to Item 10, wherein R^(4a1) isa phosphino group substituted with two substituents selected from thegroup consisting of cyclohexyl, tert-butyl, and adamantyl groups, and

R^(4a2) is a methyl group or a methoxy group.

Item 12. The production method according to any one of Items 1 to 11,wherein the reaction of step A is performed in the presence of a base.

Item 13. The production method according to Item 12, wherein the basehas a pKa of 36 to 3.6.

Item 14. The production method according to Item 12, wherein the base isat least one member selected from the group consisting of

(1) acetates, carbonates, hydrogen carbonates, phosphates, hydrogenphosphates, alkoxide salts, hydroxide salts, hydride salts, ammoniumsalts, and amide salts of alkaline or alkaline earth metals,(2) polymer-supported bases,(3) alkali metals, and(4) amines.

Item 15. A compound represented by formula (1-1):

whereinRf is a fluoro group or a perfluoroalkyl group,R^(a1) is a hydrogen atom,R^(a2) is a hydrogen atom,R^(b1) is a hydrogen atom,R^(b2) is a hydrogen atom, andR^(b3) is a C₂₋₁₁ fluoroalkyl group or a C₃₋₁₁ perfluoroalkylpolyethergroup.

Item 16. A compound represented by formula (1-2):

whereinR^(a1) is a hydrogen atom,R^(a2) is an aryl group or a heterocyclic group,R^(b1) is a hydrogen atom,R^(b2) is a hydrogen atom, andR^(b3) is a C₁₋₁₁ fluoroalkyl group.

Advantageous Effects of Invention

The present invention provides, for example, a method for synthesizing afluorovinyl ether compound from a fluorine-containing vinyl compound ata high yield.

DESCRIPTION OF EMBODIMENTS Terms

Symbols and abbreviations in the present specification can be understoodas indicating the meanings typically used in the technical field towhich the present invention pertains in accordance with the context ofthe specification, unless otherwise specified.

In the present specification, the terms “comprise” and “contain” areused with the intention of including the phrases “consist essentiallyof” and “consist of.”

Unless otherwise specified, the steps, treatments, or operationsdescribed in the present specification may be performed at roomtemperature.

In the present specification, room temperature can refer to atemperature in the range of 10 to 40° C.

In the present specification, the term “Cn-m” (wherein n and m eachrepresent a number) indicates that the number of carbon atoms is n ormore and m or less, as a person skilled in the art would usuallyunderstand.

In the present specification, unless otherwise specified, examples of“halogen atom” include fluorine, chlorine, iodine, and bromine.

In the present specification, unless otherwise specified, the term“halogeno group” includes fluoro, chloro, bromo, and iodo.

In the present specification, unless otherwise specified, the term“organic group” refers to a group formed by removing one hydrogen atomfrom an organic compound. As can be understood from this, an organicgroup contains one or more carbon atoms.

In the present specification, unless otherwise specified, the term“organic group” includes

(1) hydrocarbon groups and(2) hydrocarbon groups having one or more heteroatoms (e.g., nitrogen,oxygen, sulfur, phosphorus, halogen).

In the present specification, unless otherwise specified, the term“hydrocarbon group” refers to a group consisting only of carbon andhydrogen.

A hydrocarbon group can also be called a hydrocarbyl group.

In the present specification, unless otherwise specified, example of“hydrocarbon group” include

(1) aliphatic hydrocarbon groups optionally substituted with one or morearomatic hydrocarbon groups (e.g., benzyl group), and(2) aromatic hydrocarbon groups optionally substituted with one or morealiphatic hydrocarbon groups.

An aromatic hydrocarbon group can also be called an aryl group.

In the present specification, unless otherwise specified, the “aliphatichydrocarbon group” can have a linear, branched, or cyclic structure; ora combination thereof.

In the present specification, unless otherwise specified, the “aliphatichydrocarbon group” may be saturated or unsaturated.

In the present specification, unless otherwise specified, examples ofthe “aliphatic hydrocarbon group” include alkyl groups, alkenyl groups,alkynyl groups, and cycloalkyl groups.

In the present specification, unless otherwise specified, the “alkyl(group)” may have a linear or branched structure, or a combinationthereof.

In the present specification, unless otherwise specified, examples of“alkyl (group)” include C₁₋₁₁ linear or branched alkyl groups. Specificexamples include methyl, ethyl, propyl (e.g., n-propyl, isopropyl),butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g.,n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl),hexyl, heptyl, octyl, nonyl, and decyl.

In the present specification, unless otherwise specified, examples of“alkenyl (group)” include linear or branched alkenyl groups having 1 to10 carbon atoms. Specific examples include vinyl, 1-propenyl,isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl,2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and5-hexenyl.

In the present specification, unless otherwise specified, examples of“alkynyl (group)” include linear or branched alkynyl groups having 2 to6 carbon atoms. Specific examples include ethynyl, 1-propynyl,2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and5-hexynyl.

In the present specification, unless otherwise specified, examples of“cycloalkyl (group)” include cycloalkyl groups having 3 to 10 carbonatoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.

In the present specification, unless otherwise specified, examples of“aromatic hydrocarbon group (aryl (group))” include C₆₋₁₄ aromatichydrocarbon groups (aryl group). Specific examples include phenyl,naphthyl, phenanthryl, anthryl, and pyrenyl.

In the present specification, unless otherwise specified, examples of“aromatic hydrocarbon ring” include C₆₋₁₄ aromatic hydrocarbon rings.Specific examples includes a benzene ring, a naphthalene ring, ananthracene ring, and a phenanthrene ring.

In the present specification, unless otherwise specified, the term“alkoxy (group)” may refer to a group represented by RO— (wherein R isan alkyl group (e.g., a C₁₋₁₁ alkyl group)). Examples include C₁₋₁₁alkoxy groups (e.g., methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy, pentyloxy, and hexyloxy).

In the present specification, unless otherwise specified, the term“alkylcarbonyloxy (group)” may refer to a group represented by RCO—O—(wherein R is an alkyl group).

Specific examples include an acetoxy group.

In the present specification, unless otherwise specified, the term“ester group” refers to an organic group having at least one ester bond(i.e., —C(═O)—O— or —O—C(═O)—).

Examples of the “ester group” include

(1) groups represented by the formula: RCO₂— (wherein R is an alkylgroup), and(2) groups represented by the formula: R^(a)—CO₂—R^(b)— (wherein R^(a)is an alkyl group, and R^(b) is an alkylene group).

In the present specification, unless otherwise specified, the term“ether group” refers to a group having one or more ether bonds (—O—).

Examples of the “ether group” include polyether groups.

In the present specification, unless otherwise specified, the term“polyether group” refers to a group having two or more (e.g., 2, 3, 4,5, 6, 7, 8, or 9) ether bonds (—O—).

Examples of polyether groups include groups represented by the formula:R^(a)—(O—R^(b))_(n)— (wherein R^(a) is an alkyl group, R^(b), in eachoccurrence, is the same or different and represents an alkylene group,and n is an integer of 1 or more).

An alkylene group refers to a divalent group formed by removing onehydrogen atom from the alkyl group mentioned above.

Examples of the “ether group” also include hydrocarbyl ether groups.

The term “hydrocarbyl ether group” refers to a hydrocarbon group havingone or more ether bonds.

The “hydrocarbyl group having one or more ether bonds” may be ahydrocarbyl group having one or more ether bonds internally or at theend of the group.

Examples include alkoxy groups and benzyloxy groups.

Examples of the “hydrocarbon group having one or more ether bonds”include alkyl groups having one or more ether bonds.

The “alkyl group having one or more ether bonds” may be an alkyl groupinto which one or more ether bonds are inserted.

Such a group may also be called an alkyl ether group.

In the present specification, the prefix “perfluoro” can mean that allhydrogen are replaced by fluoro, as can be typically understood by aperson skilled in the art.

In the present specification, unless otherwise specified, the term “acyl(group)” includes alkanoyl groups.

In the present specification, unless otherwise specified, the “alkanoylgroup” refers to, for example, a group represented by RCO— (wherein R isan alkyl group).

Specific examples include acetyl.

In the present specification, unless otherwise specified, the term“cyclic group” includes cyclic aliphatic hydrocarbon groups (e.g.,cycloalkyl), aromatic hydrocarbon groups (aryl), and heterocyclicgroups.

In the present specification, unless otherwise specified, the term“heterocyclic group” includes non-aromatic heterocyclic groups andheteroaryl groups.

In the present specification, examples of “heterocyclic group” include5- to 18-membered heterocyclic groups.

In the present specification, examples of “heterocyclic group” include5- to 10-membered heterocyclic groups.

In the present specification, unless otherwise specified, a“heterocyclic group” may be monocyclic, bicyclic, tricyclic, ortetracyclic.

In the present specification, unless otherwise specified, the“heterocyclic group” may be, for example, a heterocyclic groupcontaining, in addition to carbon, 1 to 4 heteroatoms selected from thegroup consisting of oxygen, sulfur, and nitrogen as a ring-constitutingatom or ring-constituting atoms.

In the present specification, unless otherwise specified, the“non-aromatic heterocyclic group” may be saturated or unsaturated.

In the present specification, unless otherwise specified, examples of“non-aromatic heterocyclic group” include tetrahydrofuryl, oxazolidinyl,imidazolinyl (e.g., 1-imidazolinyl, 2-imidazolinyl, and 4-imidazolinyl),aziridinyl (e.g., 1-aziridinyl and 2-aziridinyl), azetidinyl (e.g.,1-azetidinyl and 2-azetidinyl), pyrrolidinyl (e.g., 1-pyrrolidinyl,2-pyrrolidinyl, and 3-pyrrolidinyl), piperidinyl (e.g., 1-piperidinyl,2-piperidinyl, and 3-piperidinyl), azepanyl (e.g., 1-azepanyl,2-azepanyl, 3-azepanyl, and 4-azepanyl), azocanyl (e.g., 1-azocanyl,2-azocanyl, 3-azocanyl, and 4-azocanyl), piperazinyl (e.g.,1,4-piperazin-1-yl and 1,4-piperazin-2-yl), diazepinyl (e.g.,1,4-diazepin-1-yl, 1,4-diazepin-2-yl, 1,4-diazepin-5-yl, and1,4-diazepin-6-yl), diazocanyl (e.g., 1,4-diazocan-1-yl,1,4-diazocan-2-yl, 1,4-diazocan-5-yl, 1,4-diazocan-6-yl,1,5-diazocan-1-yl, 1,5-diazocan-2-yl, and 1,5-diazocan-3-yl),tetrahydropyranyl (e.g., tetrahydropyran-4-yl), morpholinyl (e.g.,4-morpholinyl), thiomorpholinyl (e.g., 4-thiomorpholinyl),2-oxazolidinyl, dihydrofuryl, dihydropyranyl, and dihydroquinolyl.

In the present specification, unless otherwise specified, examples of“heteroaryl (group)” include monocyclic aromatic heterocyclic groups(e.g., 5- or 6-membered monocyclic aromatic heterocyclic groups), andaromatic fused heterocyclic groups (e.g., 5- to 18-membered aromaticfused heterocyclic groups).

In the present specification, unless otherwise specified, examples of“5- or 6-membered monocyclic aromatic heterocyclic group” includepyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, and 3-pyrrolyl), furyl (e.g.,2-furyl and 3-furyl), thienyl (e.g., 2-thienyl and 3-thienyl), pyrazolyl(e.g., 1-pyrazolyl, 3-pyrazolyl, and 4-pyrazolyl), imidazolyl (e.g.,1-imidazolyl, 2-imidazolyl, and 4-imidazolyl), isoxazolyl (e.g.,3-isoxazolyl, 4-isoxazolyl, and 5-isoxazolyl), oxazolyl (e.g.,2-oxazolyl, 4-oxazolyl, and 5-oxazolyl), isothiazolyl (e.g.,3-isothiazolyl, 4-isothiazolyl, and 5-isothiazolyl), thiazolyl (e.g.,2-thiazolyl, 4-thiazolyl, and 5-thiazolyl), triazolyl (e.g.,1,2,3-triazol-4-yl and 1,2,4-triazol-3-yl), oxadiazolyl (e.g.,1,2,4-oxadiazol-3-yl and 1,2,4-oxadiazol-5-yl), thiadiazolyl (e.g.,1,2,4-thiadiazol-3-yl and 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl(e.g., 2-pyridyl, 3-pyridyl, and 4-pyridyl), pyridazinyl (e.g.,3-pyridazinyl and 4-pyridazinyl), pyrimidinyl (e.g., 2-pyrimidinyl,4-pyrimidinyl, and 5-pyrimidinyl), and pyrazinyl.

In the present specification, unless otherwise specified, examples of“5- to 18-membered aromatic fused heterocyclic group” include isoindolyl(e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl,5-isoindolyl, 6-isoindolyl, and 7-isoindolyl), indolyl (e.g., 1-indolyl,2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, and 7-indolyl),benzo[b]furanyl (e.g., 2-benzo[b]furanyl, 3-benzo[b]furanyl,4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, and7-benzo[b]furanyl), benzo[c]furanyl (e.g., 1-benzo[c]furanyl,4-benzo[c]furanyl, and 5-benzo[c]furanyl), benzo[b]thienyl (e.g.,2-benzo[b]thienyl, 3-benzo[b]thienyl, 4-benzo[b]thienyl,5-benzo[b]thienyl, 6-benzo[b]thienyl, and 7-benzo[b]thienyl),benzo[c]thienyl (e.g., 1-benzo[c]thienyl, 4-benzo[c]thienyl, and5-benzo[c]thienyl), indazolyl (e.g., 1-indazolyl, 2-indazolyl,3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, and 7-indazolyl),benzimidazolyl (e.g., 1-benzimidazolyl, 2-benzimidazolyl,4-benzimidazolyl, and 5-benzimidazolyl), 1,2-benzisoxazolyl (e.g.,1,2-benzisoxazol-3-yl, 1,2-benzisoxazol-4-yl, 1,2-benzisoxazol-5-yl,1,2-benzisoxazol-6-yl, and 1,2-benzisoxazol-7-yl), benzoxazolyl (e.g.,2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, and7-benzoxazolyl), 1,2-benzisothiazolyl (e.g., 1,2-benzisothiazol-3-yl,1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl,1,2-benzisothiazol-6-yl, and 1,2-benzisothiazol-7-yl), benzothiazolyl(e.g., 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl,6-benzothiazolyl, and 7-benzothiazolyl), isoquinolyl (e.g.,1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, and 5-isoquinolyl),quinolyl (e.g., 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, and8-quinolyl), cinnolinyl (e.g., 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl,6-cinnolinyl, 7-cinnolinyl, and 8-cinnolinyl), phthalazinyl (e.g.,1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl,7-phthalazinyl, and 8-phthalazinyl), quinazolinyl (e.g., 2-quinazolinyl,4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, and8-quinazolinyl), quinoxalinyl (e.g., 2-quinoxalinyl, 3-quinoxalinyl,5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, and 8-quinoxalinyl),pyrazolo[1,5-a]pyridyl (e.g., pyrazolo[1,5-a]pyridin-2-yl,pyrazolo[1,5-a]pyridin-3-yl, pyrazolo[1,5-a]pyridin-4-yl,pyrazolo[1,5-a]pyridin-5-yl, pyrazolo[1,5-a]pyridin-6-yl, andpyrazolo[1,5-a]pyridin-7-yl), and imidazo[1,2-a]pyridyl (e.g.,imidazo[1,2-a]pyridin-2-yl, imidazo[1,2-a]pyridin-3-yl,imidazo[1,2-a]pyridin-5-yl, imidazo[1,2-a]pyridin-6-yl,imidazo[1,2-a]pyridin-7-yl, and imidazo[1,2-a]pyridin-8-yl).

In the present specification, examples of “aromatic group” include arylgroups, and aromatic heterocyclic groups.

1. Production Method

The production method of the present invention is a method for producinga compound represented by formula (1):

whereinRf is a fluoro group or a perfluoroalkyl group,R^(a1) is a hydrogen atom, a halogeno group, an alkyl group, afluoroalkyl group, or an aromatic group optionally having one or moresubstituents,R^(a2) is a hydrogen atom, a halogeno group, an alkyl group, afluoroalkyl group, or an aromatic group optionally having one or moresubstituents, or(i) R^(a1) and R^(a2), (ii) R^(a1) and Rf, or (iii) Rf and R^(a2) may belinked to each other,R^(b1) is R^(s),R^(b2) is a hydrogen atom or R^(s),R^(b3) is a hydrogen atom or R^(s), ortwo or three of R^(b1), R^(b2), and R^(b3), taken together with theadjacent carbon atom, may form a cyclic group optionally having one ormore substituents, andR^(s), in each occurrence, is the same or different and represents ahydrocarbon group optionally having one or more substituents (in thepresent specification, this compound may be referred to as “compound(1)”),the method comprisingstep A of reacting a compound represented by formula (2):

whereinR^(x) is a leaving group, andother symbols are as defined above (in the present specification, thiscompound may be referred to as “compound (2)”), with a compoundrepresented by formula (3):

wherein the symbols in the formula are as defined above (in the presentspecification, this compound may be referred to as “compound (3)”)in the presence of a transition metal catalyst.

The structure of the divalent group formed by linking (i) R^(a1) andR^(a2), (ii) R^(a1) and Rf, or (iii) Rf and R^(a2) is understood basedon each structure of R^(a1), R^(a2), and Rf.

Each linkage between (i) R^(a1) and R^(a2), (ii) R^(a1) and Rf, and(iii) Rf and R^(a2), may be made internally or at the end of each group.

R^(a1) is preferably a hydrogen atom, an alkyl group, an aryl group, aheterocyclic group, an alkoxy group, an alkoxycarbonyl group, acarbamoyl group, an amino group, or a cyano group.

R^(a1) is more preferably a hydrogen atom, an alkyl group, an arylgroup, a heterocyclic group, or an alkoxy group.

R^(a1) is still more preferably a hydrogen atom or an aryl group.

R^(a1) is even more preferably a hydrogen atom or a C₆₋₁₄ aryl group.

R^(a2) is preferably a hydrogen atom, an alkyl group, an aryl group, aheterocyclic group, an alkoxy group, an alkoxycarbonyl group, acarbamoyl group, an amino group, or a cyano group.

R^(a2) is more preferably an alkyl group, an aryl group, a heterocyclicgroup, or an alkoxy group.

R^(a2) is still more preferably a hydrogen atom or an aryl group.

R^(a2) is even more preferably a hydrogen atom or a C₆₋₁₄ aryl group.

R^(a2) is particularly preferably a hydrogen atom.

It is preferable that

R^(b1) be

(1) an alkyl group optionally having one or more substituents(preferably, —OH, —SH, and —NH₂ can be excluded from the substituents),(2) a cycloalkyl group optionally having one or more substituents,(3) an aryl group optionally having one or more substituents, or(4) a heterocyclic group optionally having one or more substituents(examples of the substituents include halogeno groups and alkyl groups);

R^(b2) be

(1) a hydrogen atom or(2) an alkyl group optionally having one or more substituents (examplesof the substituents include halogeno groups), and

R^(b3) be

(1) a hydrogen atom or(2) an alkyl group optionally having one or more substituents (examplesof the substituents include halogeno groups),ortwo or three of R^(b1), R^(b2), and R^(b3), taken together, may form anaromatic hydrocarbon ring optionally substituted with one or more alkylgroups.

It is more preferable that

R^(b1) be

an alkyl group optionally having one or more substituents selected fromthe group consisting of halogeno, aryl, and heteroaryl groups,

R^(b2) be

(1) a hydrogen atom or(2) an alkyl group optionally having one or more substituents (examplesof the substituents include halogeno groups), and

R^(b3) be

a hydrogen atom,ortwo or three of R^(b1), R^(b2), and R^(b3), taken together, may form aC₆₋₁₄ aromatic hydrocarbon ring optionally substituted with one or moreC₁₋₁₁ alkyl groups.

It is still more preferable that

R^(b1) be a C₁₋₁₁ alkyl group optionally having one or more substituentsselected from the group consisting of fluoro, C₆₋₁₄ aryl, and 5- to18-membered heteroaryl groups,R^(b2) be a hydrogen atom, andR^(b3) be a hydrogen atom,ortwo or three of R^(b1), R^(b2), and R^(b3), taken together, may form aC₆₋₁₄ aromatic hydrocarbon ring optionally substituted with one or moreC₁₋₁₁ alkyl groups.

It is even more preferable that

R^(b1) be a C₁₋₁₁ fluoroalkyl group (preferably a C₁₋₁₁ linearperfluoroalkyl group),R^(b2) be a hydrogen atom, andR^(b3) be a hydrogen atom.

It is preferable that

R^(a1) be a hydrogen atom, an alkyl group, a halogeno group, an arylgroup, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, acarbamoyl group, an amino group, an amide group, a cyano group, a nitrogroup, a sulfonyl group, or a sulfide group, R^(a2) be a hydrogen atom,an alkyl group, a halogeno group, an aryl group, a heterocyclic group,an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, an aminogroup, an amide group, a cyano group, a nitro group, a sulfonyl group,or a sulfide group,

R^(b1) be

(1) a hydrogen atom,(2) an alkyl group optionally having one or more substituents,(3) a cycloalkyl group optionally having one or more substituents,(4) an aryl group optionally having one or more substituents, or(5) a heterocyclic group optionally having one or more substituents,

R^(b2) be

(1) a hydrogen atom,(2) an alkyl group optionally having one or more substituents,(3) a cycloalkyl group optionally having one or more substituents,(4) an aryl group optionally having one or more substituents, or(5) a heterocyclic group optionally having one or more substituents,

R^(b3) be

(1) a hydrogen atom,(2) an alkyl group optionally having one or more substituents,(3) a cycloalkyl group optionally having one or more substituents,(4) an aryl group optionally having one or more substituents, or(5) a heterocyclic group optionally having one or more substituents,ortwo or three of R^(b1), R^(b2), and R^(b3), taken together, form analiphatic hydrocarbon ring optionally having one or more substituents,or an aromatic hydrocarbon ring optionally having one or moresubstituents.

It is more preferable that

R^(a1) be a hydrogen atom, an alkyl group, an aryl group, a heterocyclicgroup, or an alkoxy group,R^(a2) be a hydrogen atom, an alkyl group, an aryl group, a heterocyclicgroup, or an alkoxy group,

R^(b1) be

(2) a C₁₋₂₀ linear or C₃-20 branched alkyl group optionally having oneor more substituents,(3) a C₃₋₂₀ cycloalkyl group optionally having one or more substituents,(4) a C₅₋₂₀ aryl group optionally having one or more substituents, or(5) a C₅₋₂₀ heterocyclic group optionally having one or moresubstituents,

R^(b2) be

(1) a hydrogen atom,(2) a C₁₋₂₀ linear or C₃₋₂₀ branched alkyl group optionally having oneor more substituents,(3) a C₃₋₂₀ cycloalkyl group optionally having one or more substituents,(4) a C₅₋₂₀ aryl group optionally having one or more substituents, or(5) a C₅₋₂₀ heterocyclic group optionally having one or moresubstituents,

R^(b3) be

(1) a hydrogen atom,(2) a C₁₋₂₀ linear or C₃₋₂₀ branched alkyl group optionally having oneor more substituents,(3) a C₃₋₂₀ cycloalkyl group optionally having one or more substituents,(4) a C₅₋₂₀ aryl group optionally having one or more substituents,or(5) a C₅₋₂₀ heterocyclic group optionally having one or moresubstituents, ortwo or three of R^(b1), R^(b2), and R^(b3), taken together with theadjacent carbon atom, form a C₃₋₁₈ aliphatic hydrocarbon ring optionallysubstituted with one or more C₁₋₁₁ alkyl groups, or a C₅₋₁₄ aromatichydrocarbon ring optionally substituted with one or more C₁₋₁₁ alkylgroups.

It is still more preferable that

R^(a1) be a hydrogen atom, an alkyl group, a halogeno group, or an arylgroup,R^(a2) be a hydrogen atom, an alkyl group, a halogeno group, or an arylgroup,

R^(b1) be

(1) a hydrogen atom,(2) C₁₋₁₁ linear or C₃₋₁₁ branched alkyl group, optionally having one ormore substituents,(3) a C₁₋₁₁ cycloalkyl group optionally having one or more substituents,(4) a C₅₋₁₁ aryl group optionally having one or more substituents, or(5) a C₅₋₁₁ heterocyclic group optionally having one or moresubstituents,

R^(b2) be

(1) a hydrogen atom,(2) a C₁₋₁₁ linear or C₃₋₁₁ branched alkyl group optionally having oneor more substituents,(3) a C₁₋₁₁ cycloalkyl group optionally having one or more substituents,(4) a C₅₋₁₁ aryl group optionally having one or more substituents,or(5) a C₅₋₁₁ heterocyclic group optionally having one or moresubstituents,

R^(b3) be

(1) a hydrogen atom,(2) a C₁₋₁₁ linear or C₃₋₁₁ branched alkyl group optionally having oneor more substituents,(3) a C₁₋₁₁ cycloalkyl group optionally having one or more substituents,(4) a C₅₋₁₁ aryl group optionally having one or more substituents,or(5) a C₅₋₁₁ heterocyclic group optionally having one or moresubstituents, ortwo or three of R^(b1), R^(b2), and R^(b3), taken together with theadjacent carbon atom, form a C₃₋₁₅ aliphatic hydrocarbon ring or C₅₋₁₁aromatic hydrocarbon ring, each optionally having one or moresubstituents selected from the group consisting of C₁₋₁₁ alkyl and nitrogroups.

It is preferable that

R^(b1) be

a C₁₋₁₁ alkyl group optionally having one or more substituents selectedfrom the group consisting of C₆₋₁₄ aryl and 5- to 18-memberedheterocyclic groups (e.g., 5- to 18-membered non-aromatic heterocyclicgroups and 5- to 18-membered heteroaryl groups), each optionally havingone or more substituents selected from the group consisting of fluoro,keto, hydroxy, fluorovinyloxy (e.g., 1-fluorovinyloxy), ether (e.g.,C₂₋₁₁ polyether), alkoxycarbonyl, nitro, and trialkylsilyl groups,R^(b2) be a hydrogen atom, andR^(b3) be a hydrogen atom, ortwo or three of R^(b1), R^(b2), and R^(b3), taken together with theadjacent carbon atom, form a C₆₋₁₄ aromatic hydrocarbon ring optionallyhaving one or more substituents selected from the group consisting ofC₁₋₁₁ alkyl and nitro groups.

It is more preferable that

R^(a1) be a hydrogen atom,R^(a2) be a hydrogen atomR^(b1) be a hydrogen atom,R^(b2) be a hydrogen atom, andR^(b3) be a C₁₋₁₁ linear perfluoroalkyl group.R^(x) is preferably a halogeno group or a sulfonic acid ester group.

Examples of “sulfonic acid ester group” for R^(x) includemethanesulfonyloxy (OMs), benzenesulfonyloxy, p-toluenesulfonyloxy(OTs), trifluoromethanesulfonyloxy (OTf), andnonafluorobutanesulfonyloxy.

R^(x) can be more preferably a halogeno group, a mesyl group, a tosylgroup, a nosyl group, a fluorosulfonyl group, a nitro group, or a cyanogroup.

R^(x) can be more preferably a chloro group or a bromo group.

Both R^(a1) and R^(a2) are preferably hydrogen atoms in order to obtainthe effect of the present invention.

Transition Metal Catalyst

Preferable examples of transition metals in transition metal catalystsfor use in the present invention include copper, silver, gold, nickel,palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium,manganese, chromium, and zirconium.

Specifically, preferable examples of the transition metal catalyst usedin step A include copper catalysts, silver catalysts, gold catalysts,nickel catalysts, palladium catalysts, platinum catalysts, cobaltcatalysts, rhodium catalysts, iridium catalysts, iron catalysts,ruthenium catalysts, manganese catalysts, chromium catalysts, andzirconium catalysts.

More preferable examples of transition metals in transition metalcatalysts for use in the present invention include palladium, copper,silver, nickel, platinum, cobalt, and iron.

Even more preferable examples of transition metals in transition metalcatalysts for use in the present invention include palladium, copper,nickel, platinum, and iron.

Particularly preferable examples of transition metals in transitionmetal catalysts for use in the present invention include palladium.

That is, particularly preferable examples of the transition metalcatalyst for use in the present invention include palladium catalysts.

Examples of palladium catalysts for use in the present invention include

(1) zerovalent palladium complexes;(2) zerovalent palladium complexes generated from monovalent or divalentpalladium complexes during a reaction; and(3) complexes obtained by mixing these palladium complexes with at leastone compound (ligand) selected from the group consisting of ketones,diketones, phosphines, diamines, bipyridines, and phenanthrolines.

In the present specification, specific examples of zerovalent palladiumcomplexes include Pd₂(dba)₃ (dba is dibenzylideneacetone),Pd₂(dba)₃-CHCl₃, Pd(dba)₂, Pd(cod)₂ (cod is cycloocta-1,5-diene),Pd(dppe)₂ (dppe is 1,2-bis (diphenylphosphino) ethane), Pd(PCy₃)₂ (Cy iscyclohexyl), Pd(Pt-Bu₃)₂ (t-Bu is t-butyl), Pd(PPh₃)₄ (Ph is phenyl),and tris{tris[3,5-bis(trifluoromethyl)phenyl]phosphine}palladium (0).

In the present specification, examples of monovalent palladium complexesinclude palladium complexes represented by the following chemicalformula:

whereinX is a chlorine atom, a bromine atom, or an iodine atom,R, in each occurrence, is the same or different and represents a C₁₋₂₀alkyl group, a C₂₋₂₀ alkenyl group, a C₂₋₂₀ alkynyl group, or an arylgroup.

Of these, preferable specific examples includedi-μ-chlorobis(tri-tert-butylphosphine)dipalladium (I),di-μ-bromobis(tri-tert-butylphosphine)dipalladium (I),di-μ-iodobis(tri-tert-butylphosphine)dipalladium (I),di-μ-chlorobis{tri(1-adamantyl)phosphine}dipalladium (I),di-μ-bromobis{tri(1-adamantyl)phosphine}dipalladium (I), anddi-μ-iodobis{tri(1-adamantyl)phosphine}dipalladium (I).

In the present specification, specific examples of divalent palladiumcomplexes include (1) palladium chloride, palladium bromide, palladiumacetate, bis(acetylacetonato)palladium (II),dichloro(η⁴-1,5-cyclooctadiene)palladium (II),dibromo(η⁴-1,5-cyclooctadiene) palladium (II),bis(acetonitrile)dichloropalladium (II),bis(benzonitrile)dichloropalladium (II), anddi-μ-chlorobis{(q-allyl)palladium} (II); and (2) complexes obtained bybinding a phosphine ligand, such as triphenylphosphine, to thesecomplexes.

These divalent palladium complexes are, for example, reduced by areducing species (e.g., phosphines, reducing agents, and organic metalreagents) that is co-present during a reaction, thereby generatingzerovalent palladium complexes.

The above zerovalent palladium complexes or zerovalent palladiumcomplexes generated from monovalent or divalent palladium complexesthrough reduction can interact with a compound (ligand), such asketones, diketones, phosphines, diamines, bipyridines, andphenanthrolines optionally added during a reaction, and can be convertedinto zerovalent palladium complexes that are involved in the reaction.

It is not always necessary to know how many ligands are bound to azerovalent palladium complex during the reaction.

Using the above ligands, these palladium complexes are often formed intoa homogeneous solution with a reaction substrate to be used in thereaction. In addition, these palladium complexes can also be used as aheterogeneous catalyst dispersed or supported in a polymer such aspolystyrene and polyethylene.

Such heterogeneous catalysts have an advantage in processes such as acatalyst recovering process.

Specific examples of catalyst structures thereof include those in whicha metal atom is immobilized by a polymeric phosphine or the like that isa crosslinked polystyrene (PS) polymer chain having phosphine introducedthereto, as shown in the following chemical formula.

The “palladium catalyst” for use in the present invention may besupported on a carrier.

Such a supported catalyst has a cost advantage because the catalyst canbe recycled.

Examples of carriers include carbon, alumina, silica gel-alumina, silicagel, barium carbonate, barium sulfate, calcium carbonate, titaniumoxide, zirconium oxide, calcium fluoride, and zeolite.

In addition, the polymeric phosphines disclosed in the followingdocuments can also be used.

-   1) Kanbara et al., Macromolecules, 2000, vol. 33, p. 657-   2) Yamamoto et al., J. Polym. Sci., 2002, vol. 40, p. 2637-   3) JPH06-032763 Å-   4) JP2005-281454A-   5) JP2009-527352A

Examples of ketones as the ligands include dibenzylideneacetone.

Examples of diketones as the ligand include β-diketones, such asacetylacetone, 1-phenyl-1,3-butanedione, 1,3-diphenylpropanedione, andhexafluoroacetylacetone.

Preferable examples of phosphines as the ligand include dialkylmonoarylphosphines, diarylmonoalkyl phosphines, trialkylphosphines,triarylphosphines, and bidentate diphosphines.

Specific examples of dialkylmonoaryl phosphines includediisopropylphenyl phosphine, diisopropyl(o-tolyl) phosphine,diisopropyl(2,6-dimethylphenyl)phosphine, diisopropyl pentafluorophenylphosphine, di-n-butylphenyl phosphine, di-n-butyl(o-tolyl)phosphine,di-n-butyl(2,6-dimethylphenyl)phosphine, di-n-butyl pentafluorophenylphosphine, di-tert-butylphenyl phosphine,di-tert-butyl(o-tolyl)phosphine,di-tert-butyl(2,6-dimethylphenyl)phosphine, di-tert-butylpentafluorophenyl phosphine, dicyclohexyl phenylphosphine,dicyclohexyl(o-tolyl)phosphine,dicyclohexyl(2,6-dimethylphenyl)phosphine, dicyclohexylpentafluorophenyl phosphine, di(l-adamantyl)phenylphosphine,di(1-adamantyl) (o-tolyl)phosphine, di(1-adamantyl)(2,6-dimethylphenyl)phosphine, di(1-adamantyl)pentafluorophenylphosphine, 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl,2-dicyclohexylphosphino-2′1,6′-dimethoxybiphenyl,2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl,2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl,2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl,2′-dicyclohexylphosphino-2,4,6-trimethoxybiphenyl,2-dicyclohexylphosphino-2′-methylbiphenyl,2-di-tert-butylphosphino-2′-methylbiphenyl,2-di-tert-butylphosphino-2′-(N,N-dimethylamino)biphenyl,2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2′,4′,6′-triisopropyl-1,1′-biphenyl,2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl,2-di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl,(2-biphenyl)dicyclohexylphosphine, (2-biphenyl)di-tert-butylphosphine,(3R,5R)-adamantan-1-yl ((3S,5-adamantan-1-yl) ((3S,5-adamantan-1-yl))(2′,4′,6′-triisopropyl-3,6-dimethoxy-(1,1′-biphenyl)-2-yl)phosphine,2′-di-tert-butylphosphino)-3-methoxy-6-methyl-(2′,4′,6′-triisopropyl-1,1′-biphenyl,and2-(di-t-butylphosphino)-3-methoxy-6-methyl-2′,4′,6′-tri-i-propyl-1,1′-biphenyl.

Specific examples of diarylmonoalkyl phosphines includediphenylmethylphosphine, diphenylisopropylphosphine, n-butyldiphenylphosphine, tert-butyl diphenylphosphine, cyclohexyldiphenylphosphine, (1-adamantyl)diphenylphosphine,di(o-tolyl)methylphosphine, di(o-tolyl)isopropylphosphine,n-butyldi(o-tolyl)phosphine, tert-butyldi(o-tolyl)phosphine,cyclohexyldi(o-tolyl)phosphine, (1-adamantyl)di(o-tolyl)phosphine,bis(2,6-dimethylphenyl)methylphosphine,bis(2,6-dimethylphenyl)isopropylphosphine,bis(2,6-dimethylphenyl)-n-butylphosphine,bis(2,6-dimethylphenyl)-tert-butylphosphine,bis(2,6-dimethylphenyl)cyclohexylphosphine,(1-adamantyl)bis(2,6-dimethylphenyl)phosphine,bis(pentafluorophenyl)methylphosphine,bis(pentafluorophenyl)isopropylphosphine,bis(pentafluorophenyl)-n-butylphosphine,bis(pentafluorophenyl)-tert-butylphosphine,bis(pentafluorophenyl)cyclohexylphosphine, and(1-adamantyl)bis(pentafluorophenyl)phosphine.

Specific examples of trialkylphosphines include tri(C₃₋₂₀alkyl)phosphines, such as tricyclohexylphosphine, triisopropylphosphine,tri-tert-butylphosphine, trihexylphosphine, tri(1-adamantyl)phosphine,tricyclopentylphosphine, di-tert-butyl methylphosphine,cyclohexyldi-tert-butylphosphine, di-tert-butyl neopentylphosphine,di-tert-butyl isopropylphosphine, di-tert-butyl(2-butenyl)phosphine,di-tert-butyl(3-methyl-2-butenyl)phosphine,1-adamantyl-di-tert-butylphosphine, tert-butyldi(1-adamantyl)phosphine,di(1-adamantyl)isopropylphosphine, cyclohexyldi(1-adamantyl)phosphine,n-butyldi(1-adamantyl)phosphine, tribicyclo[2,2,2]octylphosphine, andtrinorbornyl phosphine.

Specific examples of triarylphosphines include tri(monocyclicaryl)phosphines, such as triphenylphosphine, trimesitylphosphine,tri(o-tolyl)phosphine, tris{(4-trifluoromethyl)phenyl}phosphine,tris(pentafluorophenyl)phosphine, andtris[3,5-bis(trifluoromethyl)phenyl]phosphine.

Specific examples of bidentate diphosphines include1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane,1,3-bis(diisopropylphosphino)propane,1,4-bis(diisopropylphosphino)butane,1,3-bis(dicyclohexylphosphino)propane,1,4-bis(dicyclohexylphosphino)butane, bis(diphenylphosphinophenyl)ether,bis(dicyclohexylphosphinophenyl)ether,1,1′-bis(diphenylphosphino)ferrocene,1,1′-bis(dicyclohexylphosphino)ferrocene,1,1′-bis(diisopropylphosphino)ferrocene,1,1′-bis(di-tert-butylphosphino)ferrocene,1,2-bis(di-tert-butylphosphinomethyl)benzene,4,6-bis(diphenylphosphino)phenoxazine,4,5-bis(diphenylphosphino)-9,9′-dimethylxanthene,4,5-bis(di-tert-butylphosphino)-9,9′-dimethylxanthene, and2,2′-bis(diphenylphosphino)-1,1′-binaphthyl.

The transition metal catalysts for use in the present invention may beused alone, or in a combination of two or more.

The phosphines used in the present invention may be tetrafluoro borates(e.g., trialkylphosphonium tetrafluoroborates, such astrihexylphosphonium tetrafluoroborate and tri-tert-butyl phosphoniumtetrafluoroborate).

Such a salt can be reacted with a base described in detail below to givea free body of phosphine (e.g., trialkylphosphine, such astricyclohexylphosphine and tri-tert-butylphosphine).

The phosphines used in the present invention may be in oxide form.

Examples of the oxide form include di(cyclo)alkylphosphine oxides (e.g.,di-tert-butylphosphine oxide and di(1-adamantyl)phosphine oxide).

Arylphosphines for heterogeneous catalysts, in which a phosphine unit isintroduced into a polymer chain, can also be preferably used.

Specific examples thereof include a triarylphosphine formed by bindingone of the phenyl groups of triphenylphosphine to a polymer chain, asshown in the chemical formula below:

Examples of diamines include tetramethylethylenediamine and1,2-diphenylethylenediamine.

Examples of bipyridines include 2,2′-bipyridyl,4,4′-dimethyl-2,2′-bipyridyl, 5,5′-dimethyl-2,2′-bipyridyl,6,6′-dimethyl-2,2′-bipyridyl, 4,4′-di-tert-butyl-2,2′-bipyridine,4,4′-dimethoxy-2,2′-bipyridyl, 2,2′-biquinoline, α,α′,α″-tripyridyl.

Examples of phenanthrolines include 1,10-phenanthroline,2-methyl-1,10-phenanthroline, 3-methyl-1,10-phenanthroline,5-methyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline,2,9-diphenyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline,5,6-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline,2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,3,4,7,8-tetramethyl-1,10-phenanthroline.

Preferred examples of the ligands include phosphines, diamines,bipyridines, and phenanthrolines.

More preferable examples of the ligands include triarylphosphines andtrialkylphosphines.

Preferred examples of triarylphosphines include triphenylphosphine andtris[3,5-bis(trifluoromethyl)phenyl]phosphine.

Preferred examples of trialkylphosphines include tricyclohexylphosphine,tri-tert-butylphosphine, triisopropylphosphine, andtri(1-adamantyl)phosphine.

Preferred examples thereof also include a triarylphosphine formed bybinding one of the phenyl groups of triphenylphosphine to a polymerchain as described above.

The palladium catalyst is preferably tris(benzylideneacetone)dipalladium or bis(benzylideneacetone) palladium.

Coordination Compound

The reaction of step A can preferably be performed in the presence of acoordination compound.

That is, the reaction of step A can be preferably performed in thepresence of the transition metal catalyst mentioned above, and acoordination compound.

The coordination compound used in step A is a compound capable offorming a coordinate bond with the transition metal catalyst (e.g.,palladium).

Examples of the coordination compound include the examples of the ligandmentioned above.

The coordination compound is particularly preferably a biphenyl compoundrepresented by formula (4-1):

whereinA⁴ is a benzene ring,A^(4b) is a benzene ring,R^(4a1) is a phosphino group substituted with two C₁ ₂₀ hydrocarbongroups,R^(4a2) is an alkyl group or an alkoxy group,R^(4a3), in each occurrence, is the same or different and represents asubstituent,R^(4b), in each occurrence, is the same or different and represents asubstituent,n4a is a number of 0 to 3, andn4b is a number of 0 to 5.

R^(4a1) is

preferably a phosphino group substituted with two substituents (whichmay be the same or different) selected from the group consisting ofsecondary C₁₋₆ alkyl, tertiary C₁₋₆ alkyl, and C₃₋₁₂ cycloalkyl groups,more preferably a phosphino group substituted with two substituents(which may be the same or different) selected from the group consistingof isopropyl, cyclohexyl, tert-butyl, and adamantyl groups,still more preferably a phosphino group substituted with twosubstituents (which may be the same or different) selected from thegroup consisting of cyclohexyl, tert-butyl, and adamantyl groups, andeven more preferably a phosphino group substituted with two substituents(which may be the same or different) selected from the group consistingof tert-butyl and adamantyl groups.

R^(4a2) is

preferably a C₁₋₆ alkyl group or a C₁₋₆ alkoxy group, more preferably anisopropyl group, a methyl group, an ethyl group, a methoxy group, or anethoxy group,still more preferably a methyl group, an ethyl group, a methoxy group,or an ethoxy group, andeven more preferably a methyl group or a methoxy group.

It is preferable that

R^(4a1) be a phosphino group substituted with two substituents selectedfrom the group consisting of cyclohexyl, tert-butyl, and adamantylgroups, andR^(4a2) be a methyl group or a methoxy group.

R^(4a3), in each occurrence, is the same or different and preferablyrepresents a C₁₋₆ alkyl group, a C₁₋₆ alkoxy group, or di(C₁₋₆alkyl)amino, and

more preferably represents a methyl group, an ethyl group, an isopropylgroup, a cyclohexyl group, a tert-butyl group, a methoxy group, anethoxy group, an isopropoxy group, or a dimethyl amino group.

R^(4b), in each occurrence, is the same or different and represents asubstituent,

preferably a C₁₋₆ alkyl group, a C₁₋₆ alkoxy group, or a di(C₁₋₆alkyl)amino, andmore preferably a methyl group, an ethyl group, an isopropyl group, acyclohexyl group, a tert-butyl group, a methoxy group, an ethoxy group,an isopropoxy group, or a dimethyl amino group.

n4a is

preferably 0 to 3,more preferably 1 to 2, andstill more preferably 1.

n4b is

preferably 0 to 5,more preferably 1 to 4, andstill more preferably 2 to 3.

In a preferable embodiment of the present invention,

A^(4a) is a benzene ring,A^(4b) is a benzene ring,R^(4a1) is a phosphino group substituted with two identical or differentC₁₋₁₀ hydrocarbon groups,R^(4a2) is a methyl group or a methoxy group,R^(4a3), in each occurrence, is the same or different and represents amethyl group or a methoxy group,R^(4b), in each occurrence, is the same or different and represents anisopropyl group,n4a is a number of 1 to 3, andn4b is a number of 2 to 3.

In a more preferable embodiment of the present invention,

A^(4a) is a benzene ring,A^(4b) is a benzene ring,R^(4a1) is a phosphino group substituted with two substituents (whichmay be the same or different) selected from the group consisting ofsecondary C₁₋₆ alkyl, tertiary C₁₋₆ alkyl, and C₃₋₁₂ cycloalkyl groups,R^(4a2) is a methyl group or a methoxy group,R^(4a3), in each occurrence, is the same or different and represents amethyl group or a methoxy group,R^(4b), in each occurrence, is the same or different and represents anisopropyl group,n4a is a number of 1 to 3, andn4b is a number of 2 to 3.

In a still more preferable embodiment of the present invention,

A^(4a) is a benzene ring,A^(4b) is a benzene ring,R^(4a1) is a phosphino group substituted with two substituents selectedfrom the group consisting of cyclohexyl, tert-butyl, and adamantylgroups,R^(4a2) is a methoxy group,R^(4a3), in each occurrence, is the same or different and represents amethyl group or a methoxy group,R^(4b), in each occurrence, is the same or different and represents anisopropyl group,n4a is 1, andn4b is 3.

Base

The reaction of step A can preferably be performed in the presence of abase.

That is, the reaction of step A can preferably be performed in thepresence of the transition metal catalyst mentioned above and a base.

The reaction of step A can preferably be performed in the presence ofthe transition metal catalyst mentioned above, the coordination compoundmentioned above, and a base.

The base is preferably a base having a pKa of preferably 36 to 3.6, morepreferably 20 to 5, and even more preferably 12 to 9.

In the present specification, pKa refers to a numerical value determinedby performing acid-base titration in water at 25° C. When a basiccompound has multiple pKa values, the maximum value is taken as the pKavalue of the basic compound.

The base is preferably at least one member selected from the groupconsisting of

(1) acetates, carbonates, hydrogen carbonates, phosphates, hydrogenphosphates, alkoxide salts, hydroxide salts, hydride salts, ammoniumsalts, and amide salts of alkaline or alkaline earth metals,(2) polymer-supported bases,(3) alkali metals, and(4) amines.

Examples of the alkoxide salts include sodium methoxide, sodiumethoxide, sodium butoxide, potassium methoxide, potassium ethoxide,potassium butoxide, lithium methoxide, and lithium ethoxide.

Examples of the hydroxide salts include sodium hydroxide, potassiumhydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide,magnesium hydroxide, calcium hydroxide, and barium hydroxide.

Examples of the hydride salts include sodium hydride, potassium hydride,lithium hydride, and calcium hydride.

Examples of the polymer-supported bases include Amberlite (trade name)resin.

Examples of the alkali metals include sodium, potassium, and lithium.

Examples of the amines include aliphatic amines, alicyclic amines,aromatic amines, and heterocyclic amines. The amines can preferably betertiary amines.

The base is preferably at least one member selected from the groupconsisting of sodium hydrogen carbonate, potassium hydrogen carbonate,sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate,potassium acetate, trimethylamine, triethylamine, pyridine, sodiummethoxide, potassium methoxide, sodium tert-butoxide, potassiumtert-butoxide, lithium hexamethyldisilazide, and lithiumdiisopropylamide.

The base is particularly preferably cesium carbonate.

The amount of the palladium catalyst used in step A may be preferably0.001 to 0.3 mol, more preferably 0.002 to 0.1 mol, and even morepreferably 0.003 to 0.05 mol, per mole of compound (2).

The target product is efficiently obtained by performing the reactionusing a palladium catalyst in this amount range.

The amount of the coordination compound used in step A may be preferably0.002 to 0.6 mol, more preferably 0.004 to 0.2 mol, and even morepreferably 0.006 to 0.1 mol, per mole of compound (2).

The target product is efficiently obtained by performing the reactionusing a coordination compound in this amount range.

The amount of the weak base used in step A may be preferably 0.5 to 5mol, more preferably 1 to 3 mol, and even more preferably 1.2 to 2 mol,per mole of compound (2).

The target product is efficiently obtained by performing the reactionusing a weak base in this amount range.

The amount of compound (3) used in step A may be preferably 0.05 to 10mol, more preferably 0.08 to 5 mol, and even more preferably 0.1 to 2mol, per mole of compound (2).

The target product is efficiently obtained by performing the reactionusing compound (3) in this amount range.

The reaction can be performed in the presence or absence of an inert gas(e.g., nitrogen gas).

The reaction of step A can be performed in the presence of or absence ofa solvent.

Examples of the solvent include aprotic solvents.

Examples of the aprotic solvent include aromatic hydrocarbons, such asbenzene, toluene, and xylene;

ethers, such as cyclopentyl methyl ether, tetrahydrofuran,bis(2-methoxyethyl)ether, and 1,2-bis(2-methoxyethoxy)ethane; lactams,such as N-methylpyrrolidone;nitriles, such as acetonitrile and propionitrile;ketones, such as acetone, ethyl methyl ketone, and isobutyl methylketone;dialkyl sulfoxides, such as dimethyl sulfoxide;tetraalkylureas, such as 1,3-dimethyl-2-imidazolidinone,dimethylpropyleneurea, and tetramethylurea;amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, andhexaalkylphosphoric triamide (e.g., hexamethylphosphoric acid amide).

These solvents may be used alone, or in a combination of two or more.

The amount of the solvent for use can be determined to be an amount thatis sufficient for the solvent to exhibit its function based on commontechnical knowledge.

The upper limit of the reaction temperature in step A can be preferably200° C., more preferably 150° C., and even more preferably 120° C.

The lower limit of the reaction temperature in step A can be preferably25° C., more preferably 50° C., and even more preferably 90° C.

The reaction temperature in step A can be preferably 25 to 200° C., morepreferably 50 to 150° C., and even more preferably 90 to 120° C.

The lower the upper limit of the reaction temperature in step A, themore likely it is that side reactions can be suppressed.

The higher the lower limit of the reaction temperature in step A, themore likely it is that the progress of the desired reaction is promoted.

The upper limit of the reaction time in step A can be preferably 48hours, more preferably 24 hours, and even more preferably 12 hours.

The lower limit of the reaction time in step A can be preferably 0.5hours, more preferably 2 hours, and even more preferably 6 hours.

The reaction time in step A can be preferably 0.5 to 48 hours, morepreferably 2 to 24 hours, and even more preferably 6 to 12 hours.

The shorter the upper limit of the reaction time in step A, the morelikely it is that side reactions can be suppressed.

The longer the lower limit of the reaction time in step A, the morelikely it is that the progress of the desired reaction is promoted.

The reaction of step A can be performed in the presence or absence of aninert gas (e.g., nitrogen gas).

The reaction of step A can preferably be performed in the presence of aninert gas (e.g., nitrogen gas).

Step A can be performed under reduced pressure, atmospheric pressure, orincreased pressure.

According to the production method of the present invention, the molaryield of the compound (1) with respect to compound (2) can preferably be50% or more, more preferably 60% or more, even more preferably 70% ormore, and still more preferably 80% or more.

The compound (1) obtained in step A can be optionally isolated orpurified by a known method, such as extraction, dissolution,concentration, precipitation, dehydration, adsorption, distillation,rectification, or chromatography; or combinations thereof.

2. Compound

Among the compounds that can be produced by the production method of thepresent invention, the following compounds are novel compounds.

The present invention also provides these compounds. These compounds canbe usefully used, for example, as a monomer for polymer production, apharmaceutical intermediate, or a pesticide intermediate.

2.1. Compound (1-1)

A compound represented by formula (1-1):

whereinRf is a fluoro group or a perfluoroalkyl group,R^(a1) is a hydrogen atom,R^(a2) is a hydrogen atom,R^(b1) is a hydrogen atom,R^(b2) is a hydrogen atom, andR^(b3) is a C₂₋₁₁ fluoroalkyl group or a C₂₋₁₁ perfluoroalkyl ethergroup.

R^(b3) is

preferably a C₂₋₁₁ perfluoroalkyl group or a C₃₋₁₁perfluoroalkylpolyether group, andmore preferably a C₂₋₁₁ linear perfluoroalkyl group or C₃₋₁₁ branchedperfluoroalkylpolyether group (the polyether group preferably has 2 to 4ether bonds (—O—)).

2.2. Compound (1-2)

A compound represented by formula (1-2):

wherein R^(a1) is a hydrogen atom, R^(a1) is a phenyl group,R^(b1) is a hydrogen atom,R^(b2) is a hydrogen atom, andR^(b3) is a C₁₋₁₁ fluoroalkyl group (preferably a C₁₋₁₁ linearperfluoroalkyl group).

The production method according to the present invention is also capableof producing compounds represented by the following formula (1-1b), inaddition to the compounds represented by the above formula (1).

The symbols in this formula may be as defined for formula (1) above.

Therefore, according to the present invention, a composition comprisinga compound represented by formula (1) above and a compound representedby formula (1-1b) above can also be produced.

The molar ratio of the compound represented by formula (1) and thecompound represented by formula (1-1b) in the composition may be, forexample, 95:5 to 90:10, 80:20 to 65:35, 60:40 to 40:60, and 10:90 to5:95.

The ratio can be adjusted by setting reaction conditions (e.g.,temperature, time).

Further, the ratio can be adjusted by purification after the compoundrepresented by formula (1) and the compound represented by formula(1-1b) are produced.

Among the compounds represented by formula (1-1b), the followingcompound is a novel compound: a compound represented by:

whereinRf is a fluoro group or a perfluoroalkyl group,R^(a1) is a hydrogen atom,R^(a2) is a hydrogen atom,R^(b1) is a hydrogen atom,R^(b2) is a hydrogen atom, andR^(b3) is a C₂₋₁₁ linear perfluoroalkyl group.

The present invention also provides this compound.

EXAMPLES

The present invention is described in more detail below with referenceto Examples. However, the present invention is not limited to theExamples.

The meanings of the symbols and abbreviations in the Examples are shownbelow.

tBuBrettPhos:2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenylBOC: tert-butoxycarbonyl group

In the examples, the term “yield” refers to isolated yield, unlessotherwise specified.

Example 1 Synthesis of β-fluoro-β-(2,2,2-trifluoroethoxy)styrene

Tris(benzylideneacetone) dipalladium (17.1 mg),2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl(24.0 mg), β-bromo-β-fluorostyrene (150 mg), and cesium carbonate (365mg) were placed in a 10-mL two-necked test tube. The container washermetically sealed and purged with nitrogen.

Toluene (2.3 mL) and 2,2,2-trifluoroethanol (112 mg) were added to thecontainer in a nitrogen atmosphere.

The container was heated at 85° C. for 1.5 hours.

After cooling the container to room temperature, the contents of thecontainer were filtered through Celite with dichloromethane and purifiedby silica gel column chromatography. The results revealed the productionof the target title vinyl ether with a molar yield of 75% with respectto β-bromo-β-fluorostyrene.

Example 2 Synthesis ofβ-fluoro-β-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptoxy)styrene

Tris(benzylideneacetone)dipalladium (17.1 mg),2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl(24.0 mg), β-bromo-β-fluorostyrene (150 mg),2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptan-1-ol (392 mg), and cesiumcarbonate (365 mg) were placed in a 10-mL two-necked test tube. Thecontainer was hermetically sealed and purged with nitrogen.

Toluene (2.3 mL) was added to the container in a nitrogen atmosphere.

The container was heated at 85° C. for 1.5 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 78%with respect to β-bromo-β-fluorostyrene (NMR). Further, the contents ofthe container were filtered through Celite with dichloromethane andpurified by silica gel column chromatography. The results revealed theproduction of the target title vinyl ether with a molar yield of 73%with respect to β-bromo-β-fluorostyrene.

Example 3 Synthesis ofβ-fluoro-β-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoroundecoxy)styrene

Tris(benzylideneacetone)dipalladium (17.1 mg),2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl(24.0 mg), β-bromo-β-fluorostyrene (150 mg),2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoroundecan-1-ol(616 mg), and cesium carbonate (365 mg) were placed in a 10-mLtwo-necked test tube. The container was hermetically sealed and purgedwith nitrogen.

Toluene (2.3 mL) was added to the container in a nitrogen atmosphere.

The container was heated at 85° C. for 4 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 72%with respect to β-bromo-β-fluorostyrene (NMR).

Example 4 Synthesis of 1-fluoro-1-(2′,2′,2′-trifluoroethoxy)ethylene

Tris(benzylideneacetone)dipalladium (4.6 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(5.8 mg), and cesium carbonate (195 mg) were placed in a 10-mLpressure-resistant container. The container was hermetically sealed andpurged with nitrogen.

Toluene (1 mL) and 2,2,2-trifluoroethanol (40 mg) were added to thecontainer in a nitrogen atmosphere.

After cooling the container to −78° C., 1-bromo-1-fluoroethylene (160mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 90%with respect to 2,2,2-trifluoroethanol (NMR).

Example 5 Synthesis of1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-11-[(1-fluorovinyl)oxy]undecane

Tris(benzylideneacetone)dipalladium (4.6 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(5.8 mg),2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-1-undecanol(220 mg), and cesium carbonate (195 mg) were placed in a 10-mLpressure-resistant container. The container was hermetically sealed andpurged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-bromo-1-fluoroethylene (90 mg)was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 80%with respect to2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-1-undecanol(NMR).

Example 6 Synthesis of1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-li-[(1-fluorovinyl)oxy]undecane

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg),2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-1-undecanol(220 mg), and cesium carbonate (195 mg) were placed in a 10-mLpressure-resistant container. The container was hermetically sealed andpurged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (230mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 76%with respect to2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-1-undecanol(NMR).

Example 7 Synthesis of 2-(1′-fluorovinyloxy)ethylbenzene

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), phenethyl alcohol (48.9 mg), and cesium carbonate (195 mg)were placed in a 10-mL pressure-resistant container. The container washermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (270mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 88%with respect to phenethyl alcohol (NMR).

Example 8 Synthesis of 2-(1′-fluorovinyloxy)ethylnaphthalene

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 2-(1-naphthyl)ethanol (68.9 mg), and cesium carbonate (195 mg)were placed in a 10-mL pressure-resistant container. The container washermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (200mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 90%with respect to 2-(1-naphthyl) ethanol (NMR).

Example 9 Synthesis of 1-tert-butyl 4-(1-fluorovinyloxy)benzene

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 4-tert-butylphenol (60.1 mg), and cesium carbonate (195 mg)were placed in a 10-mL pressure-resistant container. The container washermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container was filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the desired title vinyl ether with amolar yield of 70% with respect to 4-tert-butylphenol.

Example 10 Synthesis of 4-{(1-fluorovinyloxy)methyl}pyridine

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 4-pyridinemethanol (43.7 mg), and cesium carbonate (195 mg)were placed in a 10-mL pressure-resistant container. The container washermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (250mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 75%with respect to 4-pyridinemethanol (NMR).

Example 11

Synthesis of 2-{2-(1-fluorovinyloxy)ethyl}thiopheneTris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 2-thiophene ethanol (51.3 mg), and cesium carbonate (195 mg)were placed in a 10-mL pressure-resistant container. The container washermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (270mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of the target title vinyl ether with a molar yield of 87%with respect to 2-thiophene ethanol (NMR).

Example 12 Synthesis of1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-11-[(1-trifluoromethylvinyl)oxy]undecane

Tris(benzylideneacetone)dipalladium (9.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3-methoxy-6-methyl-1,1′-biphenyl(11.2 mg),2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-1-undecanol(220 mg), and cesium carbonate (195 mg) were placed in a 10-mLpressure-resistant container. The container was hermetically sealed andpurged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 3,3,3-trifluoropropene (210 mg)was added to the container.

The container was heated at 110° C. for 15 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were analyzed by ¹⁹F NMR, which revealedthe production of a mixture of the target title vinyl ether and aregioisomer (mixing ratio=3.3:1) with a molar yield of 24% with respectto2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoro-1-undecanol(NMR).

Example 13 Synthesis of2,2,3,3,4,4,5,5-octafluoro-6-((1-fluorovinyl)oxy)hexan-1-ol and2,2,3,3,4,4,5,5-octafluoro-1,6-bis((1-fluorovinyl)oxy)hexane

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (105 mg), and cesiumcarbonate (195 mg) were placed in a 10-mL pressure-resistant container.The container was hermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ethers; i.e.,2,2,3,3,4,4,5,5-octafluoro-6-((l-fluorovinyl)oxy)hexan-1-ol was producedwith a molar yield of 25%, and2,3,3,4,4,5,5-octafluoro-1,6-bis((1-fluorovinyl)oxy)hexane was producedwith a molar yield of 30%, with respect to2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol.

Example 14

Synthesis of 12-fluoro-2,5,8,11-tetraoxatridec-12-eneTris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), triethylene glycol monomethyl ether (66 mg), and cesiumcarbonate (195 mg) were placed in a 10-mL pressure-resistant container.The container was hermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ether with amolar yield of 61% with respect to triethylene glycol monomethyl ether.

Example 15

Synthesis of 1-(2-(1-fluorovinyl)oxy)ethyl-4-nitrobenzeneTris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 4-nitrophenethyl alcohol (66.9 mg), and cesium carbonate (195mg) were placed in a 10-mL pressure-resistant container. The containerwas hermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ether at amolar yield of 80% with respect to 4-nitrophenethyl alcohol.

Example 16 Synthesis of isobutyl 4-((1-fluorovinyl)oxy)benzoate

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), isoamyl 4-hydroxybenzoate (83.3 mg), and cesium carbonate (195mg) were placed in a 10-mL pressure-resistant container. The containerwas hermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ether with amolar yield of 30% with respect to isoamyl 4-hydroxybenzoate.

Example 17 Synthesis of N-(3-((1-fluorovinyl)oxy)propyl)phthalimide

Tris(benzylideneacetone)dipalladium (4.6 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(5.8 mg), N-(3-hydroxypropyl)phthalimide (82 mg), and cesium carbonate(195 mg) were placed in a 10-mL pressure-resistant container. Thecontainer was hermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ether with amolar yield of 60% with respect to N-(3-hydroxypropyl)phthalimide.

Example 18 Synthesis of tert-butyl4-(((1-fluorovinyl)oxy)methyl)piperidine-1-carboxylate

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 1-BOC-4-(2-hydroxyethyl)piperidine (91.7 mg), and cesiumcarbonate (195 mg) were placed in a 10-mL pressure-resistant container.The container was hermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container was filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ether with amolar yield of 83% with respect to 1-BOC-4-(2-hydroxyethyl)piperidine.

Example 19 Synthesis oftert-butyl(3-((1-fluorovinyl)oxy)propoxy)dimethylsilane

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 3-[[tert-butyl(dimethyl)silyl]oxy]-1-propanol (76.1 mg), andcesium carbonate (195 mg) were placed in a 10-mL pressure-resistantcontainer. The container was hermetically sealed and purged withnitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ether with amolar yield of 52% with respect to3-[[tert-butyl(dimethyl)silyl]oxy]-1-propanol.

Example 20 Synthesis of4-(((1-fluorovinyl)oxy)methyl)-2,2-dimethyl-1,3-dioxolane

Tris(benzylideneacetone)dipalladium (2.2 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(2.9 mg), 1,2-isopropylideneglycerol (52.9 mg), and cesium carbonate(195 mg) were placed in a 10-mL pressure-resistant container. Thecontainer was hermetically sealed and purged with nitrogen.

Toluene (1 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (170mg) was added to the container.

The container was heated at 110° C. for 12 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and purified by silica gel column chromatography. Theresults revealed the production of the target title vinyl ether with amolar yield of 47% with respect to 1,2-isopropylideneglycerol.

Example 21 Synthesis of1,1,1,2,2,3,3-heptafluoro-3-((1,1,1,2,3,3-hexafluoro-3-(1,1,1,2-tetrafluoro-3-((1-fluorovinyl)oxy)propan-2-yl)oxy)propan-2-yloxy)propane

Tris(benzylideneacetone)dipalladium (11.0 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(14.5 mg),2,3,3,3-tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)propan-1-ol(480 mg), and cesium carbonate (489 mg) were placed in a 10-mLpressure-resistant container. The container was hermetically sealed andpurged with nitrogen.

Toluene (2 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (612mg) was added to the container.

The container was heated at 110° C. for 20 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and analyzed using by ¹⁹F NMR. The results revealed theproduction of the target title vinyl ether with a molar yield of 70%with respect to2,3,3,3-tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)propan-1-ol.

Example 22 Synthesis of1,1,1,2,2,3,3-heptafluoro-3-((1,1,1,2-tetrafluoro-3-((1-fluorovinyl)oxy)propan-2-yl)oxy)propane

Tris(benzylideneacetone)dipalladium (11.0 mg),2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-biphenyl(14.5 mg), 2,3,3,3-tetrafluoro-2-(perfluoropropoxy)propoxy)propan-1-ol(320 mg), and cesium carbonate (489 mg) were placed in a 10-mLpressure-resistant container. The container was hermetically sealed andpurged with nitrogen.

Toluene (2 mL) was added to the container in a nitrogen atmosphere.

After cooling the container to −78° C., 1-chloro-1-fluoroethylene (644mg) was added to the container.

The container was heated at 110° C. for 20 hours.

After cooling the container to room temperature, the contents of thepressure-resistant container were filtered through Celite withdichloromethane and analyzed by ¹⁹F NMR. The results revealed theproduction of the target title vinyl ether with a molar yield of 65%with respect to2,3,3,3-tetrafluoro-2-(perfluoropropoxy)propoxy)propan-1-ol.

1-14. (canceled)
 15. A compound represented by formula (1-1):

wherein Rf is a fluoro group or a perfluoroalkyl group, R^(a1) is a hydrogen atom, R^(a2) is a hydrogen atom, R^(b1) is a hydrogen atom, R^(b2) is a hydrogen atom, and R^(b3) is a C₂₋₁₁ fluoroalkyl group or a C₂₋₁₁ perfluoroalkylether group.
 16. A compound represented by formula (1-2):

wherein R^(a1) is a hydrogen atom, R^(a2) is an aryl group or a heterocyclic group, R^(b1) is a hydrogen atom, R^(b2) is a hydrogen atom, and R^(b3) is a C₁₋₁₁ fluoroalkyl group.
 17. The compound according to claim 15, wherein R^(b3) is a C₂₋₁₁ perfluoroalkyl group or a C₃₋₁₁ perfluoroalkylpolyether group.
 18. The compound according to claim 15, wherein R^(b3) is a C₂₋₁₁ linear perfluoroalkyl group or C₃₋₁₁ branched perfluoroalkylpolyether group.
 19. The compound according to claim 18, wherein the polyether group has 2 to 4 ether bonds.
 20. The compound according to claim 16, wherein R^(b3) is a C₁₋₁₁ linear fluoroalkyl group. 